JP5955397B2 - New organophosphorus compounds based on anthracentriol - Google Patents

Description

  The present invention relates to bis- and trisphosphites comprising at least one structural element based on anthracentriol, and to their metal complexes, production and use of bis- and trisphosphites as polydentate compounds in catalytic reactions. .

A reaction in which an olefin compound, carbon monoxide, and hydrogen are reacted in the presence of a catalyst to obtain an aldehyde having one carbon atom is called hydroformylation or oxidation. As the catalyst in this reaction, compounds of Group 8 transition metals in the periodic table of elements, particularly rhodium and cobalt compounds are often used. Hydroformylation using rhodium compounds has the advantage of generally higher selectivity compared to catalytic reactions using cobalt, which allows the product to be obtained more economically. In the hydroformylation using a rhodium catalyst, a composition comprising rhodium and preferably a trivalent phosphorus compound as a ligand is often used. Known ligands are, for example each having a trivalent phosphorus P ^III, phosphine is a compound from the class of phosphites and phosphonites. A thorough summary of hydroformylation of olefins can be found in B. CORNILS, WA HERRMANN, “Applied Homogeneous Catalysis with Organometallic Compounds”, Vol. 1 & 2, VCH, Weinheim, New York, 1996.

  -Cobalt or rhodium based-All catalytically active compositions have inherent advantages. Therefore, as shown in the following examples, different catalytically active compositions are used depending on the substance used and the target product. When carried out using rhodium and triphenylphosphine, the α-olefin can be hydroformylated at a relatively low pressure. As the phosphorus-containing ligand, triphenylphosphine is generally used in excess, in which case a high ligand / rhodium ratio is used to increase the selectivity of the reaction to the commercially preferred n-aldehyde product. is necessary.

  Patent documents US 4,694,109 and US 4,879,416 describe bisphosphine ligands and their use in hydroformylation of olefins at low synthesis gas pressures. Particularly in the hydroformylation of propene, high activity and high n / i selectivity are achieved with this type of ligand. WO 95/30680 discloses bidentate phosphine ligands and their use in catalytic reactions, in particular in hydroformylation reactions. For example, patent documents US 4,169,861, US 4,201,714 and US 4,193,943 describe ferrocene-bridged bisphosphine as a ligand for hydroformylation.

  The disadvantage of bidentate and multidentate phosphine ligands is the relatively high cost required for their production. Therefore, such systems are often not profitable when used in industrial processes. Moreover, since the activity is relatively low, it is necessary to compensate for this by increasing the residence time. This again causes undesirable side reactions of the product.

  Rhodium-monophosphite complexes in catalytically active compositions are suitable for hydroformylation of branched olefins having internal double bonds, but are less selective for terminally oxidized compounds. From EP 0,155,508 it is known to use monophosphites substituted with bisarylenes in the rhodium-catalyzed hydroformylation of sterically hindered olefins such as isobutene.

  Catalytically active compositions based on rhodium-bisphosphite complexes are suitable for the hydroformylation of linear olefins having terminal double bonds and internal double bonds, and the products hydroformylated mainly at the end are Arise. In contrast, branched olefins having internal double bonds are converted only to a negligible extent. Although this phosphite results in a catalyst with enhanced activity when it coordinates to the transition metal center, the lifetime properties of this catalytically active composition are particularly due to the hydrolysis sensitivity of the phosphite ligand. It is not satisfactory. By using substituted bisaryl diols as building blocks of phosphite ligands, as described in EP 0,214,622 or EP 0,472,071, significant improvements can be achieved. did it.

  According to this publication, the catalytically active composition of this ligand based on rhodium is very active in the hydroformylation of α-olefins. Patent documents US Pat. No. 4,668,651, US Pat. No. 4,748,261 and US Pat. No. 4,885,401 describe products which are terminally oxidized by reacting with not only α-olefin but also 2-butene with high selectivity. Polyphosphite ligands have been described that lead to This type of bidentate ligand has also been used in the hydroformylation of butadiene (US Pat. No. 5,312,996).

  The bisphosphites disclosed in EP 1,294,731 show an olefin conversion of up to 98% during the hydroformylation of octene mixtures. Similarly, however, the desired n-selectivity for nonanal is from 36.8% up to 57.6%, and improvements are desired. This is even more important as it is estimated that the lifetime required for using a catalytically active composition in an industrial process is days instead of hours.

  Although the above bisphosphites are good ligands for rhodium hydroformylation catalysts, the development of new ligands is desired.

This new ligand is
It is desirable to exhibit high n-selectivity-and thus isomerization properties-during hydroformylation of olefins or mixtures containing olefins having internal double bonds;
-Furthermore, it has improved durability against intrinsic catalyst poisons, such as water, allowing for extended life when used in catalytically active compositions for hydroformylation. desirable;
Furthermore, it is desirable to achieve an extended lifetime when used in catalytically active compositions for hydroformylation, by inhibiting the known clustering tendency of rhodium in catalytically active compositions.

を有している本発明による化合物において、
この化合物は、少なくとも二つのＯ−Ｐ^III結合を有しており、これらのＯ−Ｐ^III結合は、同じＰ^IIIに由来していても異なるＰ^IIIに由来していてもよく、
構造要素（Ｉ）が化合物中に二つ存在する場合、これらの構造要素（Ｉ）はＣ₁₀−Ｃ_10'炭素結合を介してか、又は以下のＸ¹−Ｇ¹−Ｘ²単位：

を介して互いに結合しており、
ここで、Ｘ¹は、第一の構造要素（Ｉ）のＰ^IIIと結合しており、Ｘ²は、第二の構造要素（Ｉ）のＰ^IIIと結合しており、
Ｇ¹は、任意の他の置換基を有する、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基であり、
Ｘ¹、Ｘ²は、Ｏ、ＮＹ¹、ＣＹ²Ｙ³から選択されており、
Ｘ¹及びＸ²の意味は、互いに無関係に選択されていてよく、
Ｙ¹、Ｙ²、Ｙ³は、水素、非置換又は置換された脂肪族炭化水素基、非置換又は置換された芳香族炭化水素基から選択されており、
Ｙ¹〜Ｙ³それぞれの意味は、互いに無関係に選択されていてよく、
Ｙ¹〜Ｙ³のうち二つ以上は、互いに共有結合していてよく、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基；Ｆ、Ｃｌ、Ｂｒ、Ｉ、−ＯＲ⁸、−Ｃ（Ｏ）Ｒ⁹、−ＣＯ₂Ｒ¹⁰、−ＣＯ₂Ｍ¹、−ＳＲ¹¹、−ＳＯＲ¹²、−ＳＯ₂Ｒ¹³、−ＳＯ₃Ｒ¹⁴、−ＳＯ₃Ｍ²、−ＮＲ¹⁵Ｒ¹⁶から選択されており、
ここで、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基；−ＯＲ¹⁷から選択されており、
Ｒ¹⁷は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基から選択されており、Ｒ¹〜Ｒ¹⁷のうち二つ以上は、互いに共有結合していてよく、
Ｍ¹及びＭ²は、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウムから選択されており、かつ、
Ｍ¹及びＭ²の意味は、互いに無関係に選択されていてよいことを特徴とする、本発明による化合物により解決される。 Said task is the structural element (I):

In the compounds according to the invention having
This compound has at least two O-P ^III bonds, these O-P ^III bonds may be derived from also different P ^III have been derived from the same P ^III,
When two structural elements (I) are present in the compound, these structural elements (I) are via a C ₁₀ -C _{10 ′} carbon bond or the following X ¹ -G ¹ -X ² units:

Are connected to each other via
Wherein, X ¹ is is bonded with P ^III of the first structural element (I), X ² is coupled with P ^III of the second structural element (I),
G ¹ is a linear or branched, aliphatic, aromatic, heteroaromatic, condensed aromatic, or condensed aromatic-heteroaromatic hydrocarbon group having any other substituent. ,
X ¹ and X ² are selected from O, NY ¹ and CY ² Y ³ ,
The meanings of X ¹ and X ² may be selected independently of each other,
Y ¹ , Y ² , Y ³ are selected from hydrogen, an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group,
The meanings of Y ^{1 to} Y ³ may be selected independently of each other,
Two or more of Y ^{1 to} Y ³ may be covalently bonded to each other,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group ; F, Cl, Br, I , -OR 8, -C (O) R 9, -CO 2 R 10, -CO 2 M 1, -SR 11, -SOR 12, -SO 2 R 13, -SO 3 R ¹⁴ , —SO ₃ M ² , —NR ¹⁵ R ¹⁶ are selected,
Here, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ are hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic or heteroaromatic or fused aromatic or fused aromatic - hydrocarbon radical heteroaromatic; are selected from -OR ^17,
R ¹⁷ is selected from hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon groups, and two or more of R ^{1 to} R ¹⁷ are May be covalently linked together,
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meaning of M ¹ and M ² is solved by the compounds according to the invention, characterized in that they may be selected independently of each other.

［ここで、Ｗは、以下から選択されているものとする：
− 水素；
− 任意の他の置換基を有する、脂肪族、芳香族、複素芳香族、縮合芳香族、縮合芳香族−複素芳香族の炭化水素基；
− Ｐ^III（Ｇ²）（Ｇ³）基：

ここで、Ｇ²及びＧ³は、それぞれ、水素；任意の他の置換基を有する、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基；Ｆ、Ｃｌ、Ｂｒ、Ｉ又は−ＯＲ¹⁸、−Ｃ（Ｏ）Ｒ¹⁹、−ＣＯ₂Ｒ²⁰、−ＣＯ₂Ｍ¹、−ＳＲ²¹、−ＳＯＲ²²、−ＳＯ₂Ｒ²³、−ＳＯ₃Ｒ²⁴、−ＳＯ₃Ｍ²、−ＮＲ²⁵Ｒ²⁶から選択されており、
ここで、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基；−ＯＲ²⁷から選択されており、
Ｒ²⁷は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基；Ｆ、Ｃｌ、Ｂｒ、Ｉから選択されており、
Ｍ¹及びＭ²は、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウムから選択されており、かつ、
Ｍ¹及びＭ²の意味は、互いに無関係に選択されていてよく、
Ｇ²及びＧ³の意味は、互いに無関係に選択されていてよく、かつ、
Ｇ²とＧ³とは、互いに共有結合していてよいものとする、
− ＳｉＲ²⁸Ｒ²⁹Ｒ³⁰；ここで、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰は、水素；任意の他の置換基を有する、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基であり；Ｒ²⁸、Ｒ²⁹及びＲ³⁰の意味は、互いに無関係に選択されていてよく、Ｒ²⁸とＲ²⁹とは、互いに共有結合していてよいものとする］
を有している。 In one embodiment of the invention, the compound has the structural element (II):

[Where W is selected from:
-Hydrogen;
An aliphatic, aromatic, heteroaromatic, condensed aromatic, condensed aromatic-heteroaromatic hydrocarbon group with any other substituent;
^{- P III (G 2) (} G 3) group:

Where G ² and G ³ are each hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic or condensed aromatic or condensed aromatic having any other substituent - hydrocarbon radical heteroaromatic; F, Cl, Br, I or ^{-OR 18, -C (O) R} 19, -CO 2 R 20, -CO 2 M 1, -SR 21, -SOR 22, - Selected from SO ₂ R ²³ , —SO ₃ R ²⁴ , —SO ₃ M ² , —NR ²⁵ R ²⁶ ,
Here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are hydrogen, unsubstituted or substituted, linear or branched, hydrocarbon group of aliphatic or aromatic; are selected from -OR ^27,
R ²⁷ is selected from hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon group; F, Cl, Br, I;
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other,
The meanings of G ² and G ³ may be selected independently of each other, and
G ² and G ³ may be covalently bonded to each other.
-SiR ²⁸ R ²⁹ R ³⁰ ; where R ²⁸ , R ²⁹ , R ³⁰ are hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic with any other substituent Or the meanings of R ²⁸ , R ²⁹ and R ³⁰ may be selected independently of each other, and R ²⁸ and R ²⁹ may be It may be covalently linked]
have.

［ここで、
Ｚは、Ｇ⁴又はＸ¹−Ｇ¹−Ｘ²単位を表しており、
Ｇ⁴は、水素；任意の他の置換基を有する、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基；Ｆ、Ｃｌ、Ｂｒ、Ｉ又は−ＯＲ³¹、−Ｃ（Ｏ）Ｒ³²、−ＣＯ₂Ｒ³³、−ＣＯ₂Ｍ¹、−ＳＲ³⁴、−ＳＯＲ³⁵、−ＳＯ₂Ｒ³⁶、−ＳＯ₃Ｒ³⁷、−ＳＯ₃Ｍ²、−ＮＲ³⁸Ｒ³⁹から選択されており、
ここで、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴、Ｒ³⁵、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸、Ｒ³⁹は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基；−ＯＲ⁴⁰から選択されており、
Ｒ⁴⁰は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基から選択されており、
Ｍ¹及びＭ²は、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウムから選択されており、かつ、
Ｍ¹及びＭ²の意味は、互いに無関係に選択されていてよいものとする］
を有している。 In one embodiment of the invention, the compound has the structural element (III)

[here,
Z represents G ⁴ or X ¹ -G ¹ -X ² units;
G ⁴ represents hydrogen; a linear or branched, aliphatic, aromatic, heteroaromatic, condensed aromatic, or condensed aromatic-heteroaromatic hydrocarbon group having any other substituent ; F, Cl, Br, I or ^{-OR 31, -C (O) R} 32, -CO 2 R 33, -CO 2 M 1, -SR 34, -SOR 35, -SO 2 R 36, -SO 3 Selected from R ³⁷ , —SO ₃ M ² , —NR ³⁸ R ³⁹ ,
Here, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ are hydrogen, unsubstituted or substituted, linear or branched, An aliphatic or aromatic hydrocarbon group; selected from —OR ⁴⁰ ;
R ⁴⁰ is selected from hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon groups;
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other]
have.

［ここで、
Ｇ⁵及びＧ⁶は、水素；任意の他の置換基を有する、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基；Ｆ、Ｃｌ、Ｂｒ、Ｉ又は−ＯＲ⁴¹、−Ｃ（Ｏ）Ｒ⁴²、−ＣＯ₂Ｒ⁴³、−ＣＯ₂Ｍ¹、−ＳＲ⁴⁴、−ＳＯＲ⁴⁵、−ＳＯ₂Ｒ⁴⁶、−ＳＯ₃Ｒ⁴⁷、−ＳＯ₃Ｍ²、−ＮＲ⁴⁸Ｒ⁴⁹から選択されており、
ここで、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁷、Ｒ⁴⁸、Ｒ⁴⁹は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基；−ＯＲ⁵⁰から選択されており、
Ｒ⁵⁰は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基から選択されており、
Ｍ¹及びＭ²は、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウムから選択されており、かつ、
Ｍ¹及びＭ²の意味は、互いに無関係に選択されていてよく、
Ｇ⁵及びＧ⁶の意味は、互いに無関係に選択されていてよく、かつ、
Ｇ⁵とＧ⁶とは、互いに共有結合していてよいものとする］
を有している。 In one embodiment of the invention, the compound has the structural element (IV):

[here,
G ⁵ and G ⁶ are hydrogen; linear or branched, aliphatic or aromatic or heteroaromatic or condensed aromatic or condensed aromatic-heteroaromatic having any other substituent hydrocarbon group; F, Cl, Br, I or ^{-OR 41, -C (O) R} 42, -CO 2 R 43, -CO 2 M 1, -SR 44, -SOR 45, -SO 2 R 46, _{^{-SO 3 R 47, -SO 3 M}} 2, which is selected from -NR ⁴⁸ R ^49,
Here, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ are hydrogen, unsubstituted or substituted, linear or branched, An aliphatic or aromatic hydrocarbon group; selected from —OR ⁵⁰ ;
R ⁵⁰ is selected from hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon groups;
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other,
The meanings of G ⁵ and G ⁶ may be selected independently of each other, and
G ⁵ and G ⁶ may be covalently bonded to each other]
have.

In one embodiment of the invention, W represents a P ^III (G ² ) (G ³ ) group.

In one embodiment of the present invention, G ² and G ³ are —OR ¹⁸ .

In one embodiment of the present invention, G ⁵ and G ⁶ are —OR ⁴¹ .

In one embodiment of the present invention, X ¹ and X ² are O.

In one embodiment of the invention, G ¹ includes a bisarylene group having any other substituent.

［ここで、
Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³、Ｒ⁵⁴、Ｒ⁵⁵、Ｒ⁵⁶、Ｒ⁵⁷、Ｒ⁵⁸は、水素；任意の他の置換基を有する、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基；Ｆ、Ｃｌ、Ｂｒ又はＩ；又は−ＯＲ⁵⁹、−ＣＯＲ⁶⁰、−ＣＯ₂Ｒ⁶¹、−ＣＯ₂Ｍ¹、−ＳＲ⁶²、−ＳＯＲ⁶³、−ＳＯ₂Ｒ⁶⁴、−ＳＯ₃Ｒ⁶⁵、−ＳＯ₃Ｍ²、−ＮＲ⁶⁶Ｒ⁶⁷又はＮ＝ＣＲ⁶⁸Ｒ⁶⁹であり、
Ｒ⁵¹〜Ｒ⁵⁸それぞれの意味は、互いに無関係に選択されていてよく、かつ、Ｒ⁵¹〜Ｒ⁵⁸のうち二つ以上は、互いに共有結合していてよく、
Ｒ⁵⁹、Ｒ⁶⁰、Ｒ⁶¹、Ｒ⁶²、Ｒ⁶³、Ｒ⁶⁴、Ｒ⁶⁵、Ｒ⁶⁶、Ｒ⁶⁷は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基；−ＯＲ⁶⁸から選択されており、
Ｒ⁶⁸は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基から選択されており、
Ｍ¹及びＭ²は、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウムから選択されており、かつ、
Ｍ¹及びＭ²の意味は、互いに無関係に選択されていてよく、
ａ及びｂは、Ｘ¹及びＸ²との結合点であるものとする］
を含んでいる。 In one embodiment of the invention G ¹ is the structural element (V):

[here,
R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ are hydrogen; linear or branched, aliphatic or aromatic having any other substituent group or heteroaromatic or fused aromatic or fused aromatic - hydrocarbon radical heteroaromatic; F, Cl, Br or I; or _{^{-OR 59, -COR 60, -CO 2}} R 61, -CO 2 M 1 ^{, -SR 62, -SOR 63, -SO} 2 R 64, -SO 3 R 65, -SO 3 M 2, a -NR ⁶⁶ R ⁶⁷ or N = CR ⁶⁸ R ^69,
The meanings of R ^{51 to} R ⁵⁸ may be selected independently of each other, and two or more of R ^{51 to} R ⁵⁸ may be covalently bonded to each other.
R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ are hydrogen, unsubstituted or substituted, linear or branched, aliphatic or An aromatic hydrocarbon group; selected from -OR ⁶⁸ ;
R ⁶⁸ is selected from hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon groups;
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other,
a and b are points of attachment to X ¹ and X ² ]
Is included.

In one embodiment of the invention, G ² and G ³ are covalently bonded to each other.

［ここで、
Ｒ⁶⁹、Ｒ⁷⁰、Ｒ⁷¹、Ｒ⁷²、Ｒ⁷³、Ｒ⁷⁴、Ｒ⁷⁵、Ｒ⁷⁶は、水素；任意の他の置換基を有する、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基；Ｆ、Ｃｌ、Ｂｒ又はＩ；又は−ＯＲ⁷⁷、−ＣＯＲ⁷⁸、−ＣＯ₂Ｒ⁷⁹、−ＣＯ₂Ｍ¹、−ＳＲ⁸⁰、−ＳＯＲ⁸¹、−ＳＯ₂Ｒ⁸²、−ＳＯ₃Ｒ⁸³、−ＳＯ₃Ｍ²、−ＮＲ⁸⁴Ｒ⁸⁵又はＮ＝ＣＲ⁸⁶Ｒ⁸⁷であり、
ここで、Ｒ⁶⁹〜Ｒ⁷⁶それぞれの意味は、互いに無関係に選択されていてよく、かつ、Ｒ⁶⁹〜Ｒ⁷⁶のうち二つ以上は、互いに共有結合していてよく、
Ｒ⁷⁷、Ｒ⁷⁸、Ｒ⁷⁹、Ｒ⁸⁰、Ｒ⁸¹、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴、Ｒ⁸⁵は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基；−ＯＲ⁸⁶から選択されており、
Ｒ⁸⁶は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基から選択されており、
Ｍ¹及びＭ²は、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウムから選択されており、かつ、
Ｍ¹及びＭ²の意味は、互いに無関係に選択されていてよいものとする］
を有している。 In one embodiment of the invention, the bond G ² -G ³ has the following structural element (VI):

[here,
R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ are hydrogen; linear or branched, aliphatic or aromatic having any other substituent Group, heteroaromatic, condensed aromatic or condensed aromatic-heteroaromatic hydrocarbon group; F, Cl, Br or I; or —OR ⁷⁷ , —COR ⁷⁸ , —CO ₂ R ⁷⁹ , —CO ₂ M ^{1 , -SR 80, -SOR 81, -SO} 2 R 82, -SO 3 R 83, a _{^{-SO 3 M 2, -NR 84 R}} 85 or N = CR ⁸⁶ R ^87,
Here, the meanings of R ^{69 to} R ⁷⁶ may be selected independently of each other, and two or more of R ^{69 to} R ⁷⁶ may be covalently bonded to each other.
R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ are hydrogen, unsubstituted or substituted, linear or branched, aliphatic or An aromatic hydrocarbon group selected from -OR ⁸⁶ ;
R ⁸⁶ is selected from hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon groups;
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other]
have.

In one embodiment of the invention, G ⁵ and G ⁶ are covalently bonded to each other.

［ここで、
Ｒ⁸⁷、Ｒ⁸⁸、Ｒ⁸⁹、Ｒ⁹⁰、Ｒ⁹¹、Ｒ⁹²、Ｒ⁹³、Ｒ⁹⁴は、水素；任意の他の置換基を有する、直鎖状又は分枝鎖状の、脂肪族又は芳香族又は複素芳香族又は縮合芳香族又は縮合芳香族−複素芳香族の炭化水素基；Ｆ、Ｃｌ、Ｂｒ又はＩ；又は−ＯＲ⁹⁵、−ＣＯＲ⁹⁶、−ＣＯ₂Ｒ⁹⁷、−ＣＯ₂Ｍ¹、−ＳＲ⁹⁸、−ＳＯＲ⁹⁹、−ＳＯ₂Ｒ¹⁰⁰、−ＳＯ₃Ｒ¹⁰¹、−ＳＯ₃Ｍ²、−ＮＲ¹⁰²Ｒ¹⁰³又はＮ＝ＣＲ¹⁰⁴Ｒ¹⁰⁵であり、
ここで、Ｒ³¹〜Ｒ³⁸それぞれの意味は、互いに無関係に選択されていてよく、かつ、Ｒ⁸⁶〜Ｒ⁹³のうち二つ以上は、互いに共有結合していてよく、
Ｒ⁹⁵、Ｒ⁹⁶、Ｒ⁹⁷、Ｒ⁹⁸、Ｒ⁹⁹、Ｒ¹⁰⁰、Ｒ¹⁰¹、Ｒ¹⁰²、Ｒ¹⁰³は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基；−ＯＲ¹⁰⁴から選択されており、
Ｒ¹⁰⁴は、水素、非置換又は置換された、直鎖状又は分枝鎖状の、脂肪族又は芳香族の炭化水素基から選択されており、
Ｍ¹及びＭ²は、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウムから選択されており、かつ、
Ｍ¹及びＭ²の意味は、互いに無関係に選択されていてよいものとする］
を有している。 In one embodiment of the invention, the bond G ⁵ -G ⁶ has the following structural element (VII):

[here,
R ⁸⁷ , R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ are hydrogen; linear or branched, aliphatic or aromatic having any other substituent Group, heteroaromatic, condensed aromatic or condensed aromatic-heteroaromatic hydrocarbon group; F, Cl, Br or I; or —OR ⁹⁵ , —COR ⁹⁶ , —CO ₂ R ⁹⁷ , —CO ₂ M ^{1 , -SR 98, -SOR 99, -SO} 2 R 100, -SO 3 R 101, -SO 3 M 2, a -NR ¹⁰² R ¹⁰³ or N = CR ¹⁰⁴ R ^105,
Here, the meanings of R ^{31 to} R ³⁸ may be selected independently of each other, and two or more of R ^{86 to} R ⁹³ may be covalently bonded to each other.
R ⁹⁵ , R ⁹⁶ , R ⁹⁷ , R ⁹⁸ , R ⁹⁹ , R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ are hydrogen, unsubstituted or substituted, linear or branched, aliphatic or An aromatic hydrocarbon group; selected from -OR ¹⁰⁴ ;
R ¹⁰⁴ is selected from hydrogen, unsubstituted or substituted, linear or branched, aliphatic or aromatic hydrocarbon groups;
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other]
have.

In one embodiment of the invention, the P ^III (G ² ) (G ³ ) group corresponds to the structural formula of the P ^III (G ⁵ ) (G ⁶ ) group.

  In addition to the compounds themselves, complex compounds containing such compounds are also claimed.

In one embodiment of the present invention, the complex compound includes a compound as described above and at least one metal central atom, where the compound is the metal center via at least one P ^III It shall be coordinated to an atom.

  In one embodiment of the present invention, the metal central atom is selected from Groups 8 to 10 of the periodic table of elements.

  In one preferred embodiment of the invention, the metal central atom is rhodium.

  In addition to such complex compounds themselves, the compositions containing such complex compounds are also claimed.

  In one embodiment of the invention, the composition comprises a compound as described above and a complex compound as described above that are not coordinated to the metal central atom.

  In addition to the composition, its use is also claimed.

  In one embodiment, the composition is used as a catalytically active composition in the synthesis of organic compounds.

  In one embodiment, the composition is used as a catalytically active composition in a process for hydroformylation of an olefinically unsaturated hydrocarbon mixture.

  Furthermore, the multiphase reaction mixture is also described in the claims.

  In one embodiment, the multiphase reaction mixture is a composition as described above as an olefinically unsaturated hydrocarbon mixture, a gas mixture comprising carbon monoxide and hydrogen, an aldehyde, a catalytically active composition. Is included.

  Further, a method for hydroformylating an olefinically unsaturated hydrocarbon mixture to obtain an aldehyde is described in the claims.

In one variation, the method comprises the following method steps:
a) preparing an olefinically unsaturated hydrocarbon mixture;
b) adding a catalytically active composition as described above;
c) introducing a mixture having carbon monoxide and hydrogen;
d) heating the reaction mixture to a temperature in the range of 80-120 ° C;
e) bringing the pressure into the range of 1.0 to 6.4 MPa;
f) A step of separating the olefinically unsaturated hydrocarbon mixture after completion of the reaction.

In a variant of this method, this method is an additional method step:
g) separating the unreacted olefinically unsaturated hydrocarbon mixture and returning it to process step a).

In a variant of this method, this method is an additional method step:
h) separating the described catalytically active composition and returning it to process step b).

In a variant of this method, this method is an additional method step:
i) separating the unreacted gas mixture comprising carbon monoxide and hydrogen and returning it to process step c).

The figure which shows the test result regarding stability by NMR spectroscopy.

The following are examples of compounds according to the invention:
Examples of bidentate compounds with two phosphorus atoms according to the invention are as follows:

Examples of tridentate compounds with three phosphorus atoms according to the invention are as follows:

Examples of tetradentate compounds with four phosphorus atoms according to the invention are as follows:

Synthesis Method of Selected Compound Compound 1
A suspension of 1,8,9-anthracentriol (0.3549 g; 1.5686 mmol) in toluene (6 ml) was mixed with triethylamine (0.69 ml; 4.939 mmol) with stirring at 0 ° C. Then in small portions, 4,8-di-tert-butyl-6-chloro-2,10-dimethoxydibenzo [d, f] [1,3,2] dioxa-phosphine (1.3267 g; in toluene (15 ml); 3. 1372 mmol). Stir overnight, filter and concentrate the filtrate to dryness in vacuo. The residue dried at 40 ° C. and 0.1 KPa for 2 hours is purified by column chromatography (developing solvent: dichloromethane, R _f = 0.62).

Compound 2
A suspension of 1,8,9-anthracentriol (1.076 g; 4.755 mmol) in toluene (18 ml) was mixed with triethylamine (2.09 ml; 14.973 mmol) with stirring and then 0. In small portions at 0 ° C., 2,4,8,10-tetra-tert-butyl-6-chlorodibenzo [d, f] [1,3,2] dioxaphosphine (4.518 g) in toluene (45 ml). ; 9.511 mmol). Stir at room temperature overnight, stir for an additional 2 hours at 70 ° C., filter, and concentrate the filtrate to dryness in vacuo. The residue is purified by column chromatography (developing solvent hexane / dichloromethane = 1: 2, R _f = 0.72) to obtain a crude yield of 4.27 g (3.869 mmol, 81%). Pure material is obtained by recrystallization from hot acetonitrile.

Compound 3
A suspension of anthracentriol (0.629 g; 2.782 mmol) in toluene (14 ml) was mixed with triethylamine (0.866 g; 8.76 mmol) with stirring at 0 ° C. and then in small portions with toluene ( 26 ml) solution of 4,8-di-tert-butyl-2,6,10-trichlorodibenzo [d, f] [1,3,2] dioxaphosphine (2.611 g; 5.563 mmol) Mix with. Stir overnight, filter and concentrate the filtrate to dryness in vacuo. Recrystallization from hexane (65 ml) gave a concentrated product (ca. 85%) that was used for further synthesis.

Compound 4
Under stirring, a solution of 1,8,9-anthracentriol (0.207 g; 0.928 mmol) and triethylamine (0.294 g; 2.92 mmol) in toluene (10 ml) was added in portions at −20 ° C. , Mixed with a solution from compound 24 (0.882 g; 0.928 mmol) in toluene (10 ml). After stirring overnight at room temperature, the reaction solution is filtered and the filtrate is concentrated to dryness in vacuo. The solid obtained is dried at 50 ° C. and 0.1 KPa for 2 hours and recrystallized from acetonitrile (100 ml).

Compound 5
A solution of 1,8,9-anthracentriol (0.538 g; 2.378 mmol) and triethylamine (0.757 g; 7.49 mmol) in toluene (20 ml) was added in portions with stirring to toluene (30 ml). Mix with a solution from 21 (2.011 g; 2.378 mmol) in -20 ° C. After stirring overnight at room temperature, the reaction solution is filtered and the filtrate is concentrated to dryness in vacuo. The resulting solid is dried at 50 ° C. and 0.1 KPa for 2 hours and purified by column chromatography (eluent: dichloromethane, R _f = 0.46 and 0.51, two diastereoisomers).

Compound 6
A solution from 5 (0.994 g; 0.995 mmol) in THF (7 ml) is mixed with hexamethyldisilazane (0.802 g; 4.98 mmol) dissolved in THF (12 ml). The reaction solution is heated under reflux for 10 hours and then concentrated to dryness in vacuo. The obtained solid is dried at 50 ° C. and 0.1 KPa for 2 hours. The residue is recrystallized from hexane.

Compound 7
A solution of 1 (0.966 g; 0.967 mmol) in toluene (12 ml) was mixed with triethylamine (0.42 ml; 3.035 mmol) with stirring at room temperature and then at 0 ° C. in toluene (4 ml). Of 2-chloro-4H-benzo [d] [1,3,2] dioxaphosphinin-4-one (0.196 g; 0.967 mmol). Heat to room temperature, stir overnight and filter. The filtrate is concentrated to dryness in vacuo, the residue is dried at 40 ° C. and 0.1 KPa for 3 hours and then purified by column chromatography (developing solvent hexane / dichloromethane, 1:10, R _f = 0.8).

Compound 8
A solution of 1 (2.0 g; 2.002 mmol) in toluene (20 ml) was mixed with triethylamine (0.88 ml; 6.314 mmol) with stirring at room temperature, then at 0 ° C. in toluene (7 ml). Of 2-chloro-4H-naphtho [1,2-d] [1,3,2] dioxaphosphinin-4-one (0.656 mg; 2.602 mmol). Heat to room temperature, stir overnight and filter. The filtrate is concentrated to dryness in vacuo and the residue is dried at 50 ° C. and 0.1 KPa for 1 hour and then purified by column chromatography (developing solvent hexane / dichloromethane, 1:10, R _f = 0.62).

Compound 9
A solution of 2 (1.329 g; 1.204 mmol) in toluene (15 ml) was mixed with triethylamine (0.53 ml; 3.781 mmol) with stirring at room temperature, then at 0 ° C. in toluene (5 ml). Of 2-chloro-4H-benzo [d] [1,3,2] dioxaphosphinin-4-one (0.243 mg; 1.204 mmol). Heat to room temperature, stir for 48 hours and filter. The filtrate is concentrated to dryness in vacuo and the residue is dried at 50 ° C. and 0.1 KPa for 1 hour and then purified by column chromatography (developing solvent hexane / dichloromethane, 2: 1, R _f = 0.22).

Compound 10
a) 2-Chloro-4H- [1,3,2] dioxaphosphinino [4,5-b] pyridin-4-one, which is a chlorophosphite from 2-hydroxynicotinic acid

A solution of 2-hydroxynicotinic acid (0.5 g; 3.594 mmol) and triethylamine (1.5 ml; 10.783 mmol) in THF (20 ml) was stirred with PCl ₃ dissolved in THF (8 ml). (0.494 g; 3.594 mmol) at -20 ° C. After stirring at room temperature overnight and further stirring at 70 ° C. for 2 hours, the reaction solution is filtered and the solid is washed with THF (5 ml). The filtrate is concentrated to dryness in vacuo and the yellow residue is dried at 50 ° C. and 0.1 KPa for 1 hour. Yield: 0.519 g (2.550 mmol; 71%). The solid had a purity of 95 mol% according to NMR spectroscopy and was used in the next synthesis step without further purification.

b) Conversion to compound 10 A solution of 1 (1.859 g; 1.861 mmol) in toluene (22 ml) was mixed with triethylamine (0.82 ml; 5.869 mmol) with stirring at room temperature and then at 0 ° C. A solution of 2-chloro-4H- [1,3,2] dioxaphosphinino [4,5-b] pyridin-4-one (0.4544 g; 2.233 mmol) in toluene (14 ml) Mix. Heat to room temperature, stir overnight, filter, and wash the filter cake with THF (4 ml × 2). The combined filtrates are concentrated to dryness in vacuo and dried at 50 ° C. and 1 mbar for 3 hours. The residue is stirred overnight with 50 ml of hexane. Filter, remove the solvent in vacuo, and dry the resulting solid mass at 70 ° C. and 0.1 KPa for 5 hours.

Compound 11
A solution of 22 (2.135 g; 1.941 mmol) in toluene (18 ml) was mixed with triethylamine (1.08 ml; 7.765 mmol) with stirring at room temperature and then at 0 ° C. , 9-anthracentriol (0.439 g; 1.941 mmol). Heat to room temperature, stir overnight, filter, remove the solvent in vacuo and dry at 50 ° C. and 0.1 KPa for 5 hours.

Compound 12
A solution of 22 (1.082 g; 0.983 mmol) in toluene (10 ml) was mixed with triethylamine (0.55 ml; 3.934 mmol) with stirring at room temperature, then at 0 ° C., solid anthracenediol- 1,9 (0.207 g; 0.983 mmol). Heat to room temperature and stir overnight, then stir at 70 ° C. for 2 hours, filter, remove the solvent in vacuo and dry at 60 ° C. and 0.1 KPa for 4 hours. The residue is purified by column chromatography (dichloromethane / hexane = 1: 1, R _f = 0.27).

Compound 13
A solution of 11 (0.674 g; 0.537 mmol) in THF (4 ml) was mixed in portions with a solution from hexamethyldisilazane (0.433 g; 2.689 mmol) in THF (8 ml) and refluxed. Boil down for 14 hours, then concentrate to dryness. The residue is purified by column chromatography (eluent hexane / dichloromethane, 1: 2, R _f = 0.47).

Compound 14
A solution of 23 (0.47 g; 0.390 mmol) and triethylamine (0.158 g; 1.561 mmol) in toluene (5 ml) at 0 ° C. as a solid 1,8,9-anthracentriol (0. 088 g; 0.390 mmol). After stirring at room temperature overnight and further stirring at 70 ° C. for 2 hours, the reaction solution is filtered and the filtrate is concentrated to dryness in vacuo. The residue is purified by column chromatography (eluent hexane / dichloromethane, 2: 1, R _f = 0.4).

Compound 15
A solution of 3 (1.479 g; 1.455 mmol) and triethylamine (0.462 g; 4.568 mmol) in toluene (20 ml) was stirred with 2-chloro-4H-benzoate in toluene (10 ml). [D] Stir at 0 ° C. with a solution from [1,3,2] dioxaphosphinin-4-one (0.338 g; 1.673 mmol). After stirring overnight at room temperature, the reaction solution is filtered and the filtrate is concentrated to dryness in vacuo. The resulting solid is dried at 50 ° C. and 0.1 KPa for 2 hours and recrystallized from acetonitrile for purification.

Compound 16
A solution from 5 (0.999 g; 1 mmol) in toluene (12 ml) was mixed with triethylamine (0.53 ml; 3.781 mmol) with stirring at room temperature and then at 0 ° C. in toluene (4 ml). Mix with a solution from 2-chloro-4H-benzo [d] [1,3,2] dioxaphosphinin-4-one (0.203 g; 1 mmol). Heat to room temperature, stir overnight and filter. The filtrate is concentrated to dryness in vacuo, the residue is dried at 40 ° C. and 0.1 KPa for 3 hours and then purified by column chromatography (developing solvent hexane / dichloromethane, 1:10, R _f = 0.8).

Compound 17
To a solution of 1 (1.487 g, 1.487 mmol) and triethylamine (0.472 g; 4.673 mmol) in toluene (17 ml) at 0 ° C. in 2-chloronaphtho [1,8 in toluene (10 ml). Add a solution from -de] [1,3,2] dioxaphosphinine (0.333 g; 1.489 mmol). After stirring overnight at room temperature, the reaction solution is filtered and the filtrate is concentrated to dryness in vacuo. The solid obtained is dried at 50 ° C. and 0.1 KPa for 2 hours and recrystallized from acetonitrile (20 ml).

Compound 18
A solution of 1 (1.289 g; 1.289 mmol) in THF (12 ml) is mixed at −20 ° C. with an equimolar amount of n-BuLi in hexane (5 ml). Heat to room temperature and stir overnight, and the mixture thus obtained is stirred at 0 ° C. with 4,8-di-tert-butyl-6-chloro-2,10-dimethoxydibenzoate in THF (9 ml). Add to a solution of [d, f] [1,3,2] dioxa-phosphapine (0.545 g; 1.289 mmol). The mixture is stirred at room temperature for 16 hours and concentrated to dryness in vacuo. The residue is stirred with toluene (12 ml), filtered, and the filtrate is concentrated to dryness in vacuo and dried at 50 ° C. and 0.1 KPa for 3 hours.

Compound 19
a) Dimeric anthracentriol according to W. Geiger, Chem. Ber. 1974, 107, 2976-2984 b) A suspension of anthracentriol dimer (0.298 g; 0.6615 mmol) in toluene (2 ml) Under stirring, mixed with triethylamine (0.29 ml; 2.083 mmol) and then in portions at 0 ° C. in 4,8-di-tert-butyl-6-chloro-2,10-in toluene (10 ml). Mix with a solution of dimethoxydibenzo [d, f] [1,3,2] dioxaphosphine (1.119 g; 2.646 mmol). Stir overnight at room temperature, stir for an additional 6 hours at 70 ° C., filter, wash the frit residue with hot toluene (5 ml) and concentrate the filtrate to dryness in vacuo. Crude yield: 0.589 g (0.295 mmol, 44%). After stirring with acetonitrile (10 ml), filtering, the frit residue is taken up in THF (5 ml) and crystallization occurs after addition of acetonitrile (8 ml). The resulting solid is dried in vacuo.

Compound 20 (x2 toluene)
A suspension of anthracentriol dimer (0.400 g; 0.888 mmol) in toluene (28 ml) is mixed with triethylamine (0.4 ml; 2.892 mmol) with stirring and then a small amount at −20 ° C. Each of 21,4,8-di-tert-butyl-6- (3,3′-di-tert-butyl-2 ′-(dichlorophosphinooxy) -5,5′-dimethoxy in toluene (32 ml) Mix with a solution of biphenyl-2-yloxy) -2,10-dimethoxydibenzo [d, f] [1,3,2] dioxaphosphine (1.488 g; 1.776 mmol). Stir at room temperature overnight, further stir at 70 ° C. for 2 hours, filter, concentrate the filtrate to dryness in vacuo, and dry the residue at 50 ° C. and 0.1 KPa for 2.5 hours. The resulting solid is stirred with acetonitrile (40 ml) overnight, filtered and dried at 50 ° C. and 0.1 KPa for 4 hours.

Compound 21
4,8-di-tert-butyl-6- (3,3′-di-tert-butyl-2 ′-(dichlorophosphinooxy) -5,5′-dimethoxybiphenyl-2-yloxy) -2,10 -Dimethoxy-dibenzo [d, f] [1,3,2] dioxaphosphine 3,3'-di-tert-butyl-2 '-(4,8-di-tert- in toluene (133 ml) Butyl-2,10-dimethoxydibenzo [d, f] [1,3,2] dioxaphosphin-6-yloxy) -5,5′-dimethoxybiphenyl-2-ol (D. Selent, D. Hess , K.-D. Wiese, D. Roettger, C. Kunze, A. Boerner, Angew. Chem. 2001, 113, 1739) (11.37 g; 15.26 mmol) and triethylamine (3.09 g; 30.54 mmol). ) And dissolved in toluene (17 ml) with stirring. Stir with PCl ₃ (2.51 g; 18.31 mmol) at 0 ° C. After stirring at room temperature overnight and further stirring at 85 ° C. for 3.5 hours, the reaction solution is filtered and the filtrate is concentrated to dryness in vacuo. The residue is dried for 2.5 hours at 60 ° C. and 1 mbar, then dissolved in hexane (125 ml) and left at 5 ° C. overnight. The resulting crystalline material is filtered, washed with cold hexane (20 ml) and dried.

Compound 22
A solution of 1 (1.0 g; 1.001 mmol) in toluene (6 ml) was mixed with triethylamine (0.28 ml; 2.002 mmol) with stirring at room temperature, then at 0 ° C. in toluene (2 ml). With a solution of phosphorus trichloride (0.152 g, 1.1 mmol). Heat to room temperature, stir overnight, filter, and remove the solvent in vacuo. The residue is stirred with 10 ml of hexane for 16 hours, filtered and dried at 50 ° C. and 0.1 KPa for 3 hours.

Compound 23
A solution of 2 (0.6 g; 0.545 mmol) and triethylamine (0.109 g; 1.087 mmol) in toluene (9 ml) was added in portions with stirring to PCl ₃ (0. 070 g; 0.516 mmol) and mixed at 0 ° C. After stirring overnight at room temperature, the reaction solution is filtered and the filtrate is concentrated to dryness in vacuo. The residue was dried at 50 ° C. and 0.1 KPa for 3 hours and used in the next synthesis step without further purification.

Compound 24
Compound 24 was prepared in the same manner as 21 with the corresponding phosphite phenol (D. Selent, D. Hess, K.-D. Wiese, D. Roettger, C. Kunze, A. Boerner, Angew. Chem. 2001, 113, 1739) and PCl ₃ . The crude product was washed with hexane and dried at 50 ° C. and 0.1 KPa for 2 hours, after which pure material was obtained by spectroscopy.

And test ligand 17 Stability by NMR spectroscopy, and Bifehosu a comparative ligand bidentate, respectively dissolved in toluene D ₈ untreated transferred to NMR tubes and sealed. Over 32 days, the ligand content was followed by NMR spectroscopy.

  The results are shown in FIG. As can be clearly seen in FIG. 1, ligand 17 has a much higher stability than the comparative ligand bifefos. For example, the comparative ligand bifefos is no longer detectable by NMR techniques after 32 days, whereas ligand 17 was measured at a concentration of 60% relative to the initial value.

  From this stability test for the respective free ligand 17 and bifephos, it is possible to directly infer the stability for the corresponding catalytically active composition, for example from rhodium complex derivatives formed therefrom. That is, for hydroformylation processes operated with these catalytically active compositions, the lifetime of catalytically active compositions based on ligand 17 is clearly extended and thus economically optimized. This does not require the addition of other components having a stabilizing action, for example -disclosed in EP 2,280,920--sterically demanding amine derivatives. The technical teaching is demonstrated in detail by the following catalytic reaction tests using various olefins or various olefin-containing hydrocarbon streams.

A rhodium complex was prepared from the exemplary structural ligand 17 of tridentate properties and could be isolated with quality compatible with X-rays. The structure estimated from the X-ray photograph is shown below.

The resulting data support the three-coordinate of P ^III to rhodium. Therefore, there is a potentially relatively high ^PIII concentration on the transition metal in solution, so that
Rhodium is better retained in solution, and in the form of a catalytically active composition, and
-Rhodium cluster formation known from the literature is suppressed.

  Ligand dissociation and cluster formation are less preferential than in the bidentate system, and the lifetime of the catalytically active composition is longer.

A rhodium complex was prepared from an exemplary structural ligand 17 of the tridentate characteristic of the binuclear structure and could be isolated with a quality suitable for X-rays. The structure deduced from the radiograph is shown below:

  The data obtained supports the structure of the binuclear rhodium complex in the catalytically active composition. This demonstrates stabilization of the second rhodium atom per complex in the catalytically active composition, and thus prevents rhodium clustering, i.e., rhodium loss.

Among the requirements for the new ligands mentioned at the beginning,
The point of improved durability against intrinsic catalyst poisons, and the formation of binuclear complexes and ligands by multiple coordination with tridentate ligands and by the provision of the compounds according to the invention The use of it suppresses the formation of rhodium clusters.

  The ability of the compounds according to the invention when used as ligands in catalytically active compositions for hydroformylation with isomerization is disclosed in the following catalytic reaction tests on olefins and olefin-containing mixtures.

Catalytic Reaction Test Procedure Hydroformylation was carried out in a 200 ml autoclave equipped with a constant pressure retainer, gas flow meter, gas feed stirrer and pressure pipette. In order to minimize the effects of moisture and oxygen, not only the solvent (Tol is toluene, PC is propylene carbonate, THF is tetrahydrofuran) as well as the substrate was dried. For testing, [(acac) Rh (COD)] (acac is an acetylacetonate anion and COD is 1,5-cycloocta as a catalyst precursor in toluene in an autoclave under an argon atmosphere. A solution of rhodium in the form of a diene) was charged. The phosphite compound dissolved in toluene was then mixed in a substantial amount, usually 2-5 ligand equivalents per rhodium. The mass of toluene added each time was weighed. Weight of olefin: 1-octene (10.62 g; 94.64 mmol), n-octene (10.70 g; 95.35 mmol), 2-pentene (2.81 g; 40.0 mmol (in the table below ( P)), or 9.75 g; 139.00 mmol). The addition of 1-butene, 2-butene and isobutene is performed in the same manner. The autoclave is a) 4.2 MPa if the final pressure is 5.0 MPa; b) 1.2 MPa if the final pressure is 2.0 MPa; and c) 0.2 MPa if the final pressure is 1.0 MPa. Each was heated to the indicated temperature under stirring (1500 rpm) at 7 MPa total gas pressure (syngas: H ₂ (99.999%): CO ₂ (99.997%) = 1: 1). After reaching the reaction temperature, the synthesis gas pressure is a) to 4.85 MPa if the final pressure is 5.0 MPa; b) to 1.95 MPa if the final pressure is 2.0 MPa; and c) final. When the pressure is 1.0 MPa, the pressure is increased to 0.95 MPa. Each of the olefins or olefin-containing mixtures shown in the table is pressurized with an overpressure of about 0.3 MPa set in a pressure pipette. The reaction was carried out at a constant pressure of 5.0, 2.0 to 1.0 MPa for 4 hours, respectively. After the reaction time had elapsed, the autoclave was cooled to room temperature, released under stirring and purged with argon. Immediately after switching off the stirrer, 1 ml of each reaction mixture was removed, diluted with 5 ml of pentane and analyzed by gas chromatography: HP 5890 Series II plus, PONA, 50 m × 0.2 mm × 0.5 μm. The amount of residual olefin and aldehyde was measured against toluene solvent as an internal standard.

Contact reaction test using compounds 6-17
Ausb. Represents the yield based on the olefin or olefin-containing mixture used.

  Sel. (%) Represents n-selectivity (%).

  All the ligands used are tridentate and show good to excellent yields in conversion, as well as excellent n-selectivity in each case. As indicated by the L / Rh ratio in the table, the ligand excess required by each catalytically active composition to achieve such results is negligible.

  All the ligands used are tridentate and show good to excellent yields in conversion, as well as excellent n-selectivity in each case. As indicated by the L / Rh ratio in the table, the ligand excess required by each catalytically active composition to achieve such results is negligible. As is evident in the example of ligand 7 in the table, a higher degree of ligand excess is not necessary.

These detailed series of catalytic reaction tests using 2-pentene have two characteristics over other series of tests:
When using a bidentate compound with ligand 6, there is a clear yield drop compared to the other ligands used;
・ In a test using tridentate ligand 7 in combination with a highly sterically demanded amine derivative-trademark TINUVIN ^(R) sebacic acid di-4 (2,2,6,6-tetramethylpiperidinyl) ester- In this case, no improved results are obtained in terms of yield and n-selectivity.

Claims (12)

The following compounds (i) to (iii)
(I) Structural element (III):

[here,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are hydrogen,
Z is -OR ³¹ and
W is a P ^III (G ² ) (G ³ ) group, and G ² and G ³ are bonded,
R ³¹ is a substituted 2-biphenyl group ;
G ² -G ³ is the structural element (VI):

[here,
R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ are hydrogen; linear or branched, aliphatic carbonized with any other substituent Hydrogen group; F, Cl, Br or I; or —OR ⁷⁷ , —COR ⁷⁸ , —CO ₂ R ⁷⁹ , —CO ₂ M ¹ , —SR ⁸⁰ , —SOR ⁸¹ , —SO ₂ R ⁸² , —SO ₃ R ^83, -SO ₃ M ^2, or a -NR ⁸⁴ R ^85,
Here, the meanings of R ^{69 to} R ⁷⁶ may be selected independently of each other,
R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ are hydrogen, unsubstituted or substituted, linear or branched, aliphatic Selected from hydrocarbon groups,
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other]
Together with R ^1, R ^2, the position of the ^{R 3, R 5, R 6} , structural elements of R ⁷ is hydrogen and the (III) is R ⁴ compounds represented, or in the structural element (III) by Bound compounds,
(Ii) Structural element (IV):

[here,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are hydrogen,
X ¹ and X ² are O,
G ¹ is the structural element (V):

[here,
R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ are hydrogen; linear or branched, aliphatic carbonized with any other substituent hydrogen radical; F, Cl, Br or I; or _{^{-OR 59, -COR 60, -CO 2}} R 61, -CO 2 M 1, -SR 62, -SOR 63, -SO 2 R 64, -SO 3 R ^65, a -SO ₃ M ² or -NR ⁶⁶ R ^67,
The meanings of R ^{51 to} R ⁵⁸ may be selected independently of each other,
R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ are hydrogen, unsubstituted or substituted, linear or branched, aliphatic Selected from hydrocarbon groups,
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other,
a and b are points of attachment to X ¹ and X ² ]
Represented by
G ⁵ and are bonded with each G ^6, G ⁵ -G ⁶ is,
・ The following formula

[Wherein, said R 'is, H, OH or OSi (CH _{3) 3} is selected from' the group represented by (wherein, binds to ^{P III} at the position 1, 9 O-),
・ Structural element (VII)

[here,
R ⁸⁷ , R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ are hydrogen; linear or branched, aliphatic carbonized with any other substituent Hydrogen group; F, Cl, Br or I; or —OR ⁹⁵ , —COR ⁹⁶ , —CO ₂ R ⁹⁷ , —CO ₂ M ¹ , —SR ⁹⁸ , —SOR ⁹⁹ , —SO ₂ R ¹⁰⁰ , —SO ₃ R ^101, -SO ₃ M ^2, or a -NR ¹⁰² R ^103,
Here, the meanings of R ^{87 to} R ⁹⁴ may be selected independently of each other,
R ⁹⁵ , R ⁹⁶ , R ⁹⁷ , R ⁹⁸ , R ⁹⁹ , R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ are hydrogen, unsubstituted or substituted, linear or branched, aliphatic Selected from hydrocarbon groups,
M ¹ and M ² are selected from alkali metals, alkaline earth metals, ammonium, phosphonium, and
The meanings of M ¹ and M ² may be selected independently of each other]
・ The following formula

A group represented by (wherein, binds to ^{P III} in 1,8-position of the O-),
・ The following formula

A group represented by
・ The following formula

A group represented by
・ The following formula

Group represented by
And
W is H, Si (CH ₃ ) ₃ , P ^III (G ² ) (G ³ ) group (G ² and G ³ are bonded), or

Is]
Or in the structural element (VI), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ are hydrogen and the structural element (VI) is at the position of R ⁴ Compounds bonded to each other,
(Iii) Structural element (I):

[here,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are hydrogen,
O at the 1st and 8th positions of the structural element (I) is bonded to the P ^III (G ² ) (G ³ ) group, and G ² and G ³ are bonded;
G ² -G ³ is the structural element (VI)],
And the structural element (I) is bonded to each other at the position of R ⁴ . Less than:
A compound according to claim 1 ,
-In complex compounds containing at least one metal central atom,
A compound according to claim 1, characterized in that coordinated to the metal central atom via at least one of P ^III, complex compounds. The complex compound according to claim 2 , wherein the metal central atom is selected from Groups 8 to 10 of the periodic table of elements. The complex compound according to claim 3 , wherein the metal central atom is rhodium. In the composition:
- not coordinated to the metal central atom, the compounds according to claim 1, and - characterized in that it comprises a complex compound according to any one of claims 2 to 4, the composition. Use of the composition according to claim 5 as catalytically active composition in the synthesis of organic compounds. Use of the composition according to claim 5 as catalytically active composition in the hydroformylation process of olefinically unsaturated hydrocarbon mixtures. In a multiphase reaction mixture, the following:
-Olefinically unsaturated hydrocarbon mixtures,
A gas mixture containing carbon monoxide and hydrogen,
-Aldehydes,
A multiphase reaction mixture, characterized in that it comprises the composition according to claim 5 as a catalytically active composition; In the process of hydroformylating an olefinically unsaturated hydrocarbon mixture to obtain an aldehyde, the following process steps:
a) preparing an olefinically unsaturated hydrocarbon mixture;
b) adding the catalytically active composition according to claim 5 ;
c) introducing a mixture having carbon monoxide and hydrogen;
d) heating the reaction mixture to a temperature in the range of 80-120 ° C;
e) bringing the pressure into the range of 1.0 to 6.4 MPa;
f) A process comprising separating the olefinically unsaturated hydrocarbon mixture after completion of the reaction. Another method step:
The process according to claim 9 , comprising the step of g) separating the unreacted olefinically unsaturated hydrocarbon mixture and returning it to process step a). Another method step:
The process according to claim 9 or 10 , comprising the step of h) separating the catalytically active composition according to claim 5 and returning it to process step b). Another method step:
12. A process according to any one of claims 9 to 11 , comprising the step of i) separating the unreacted gas mixture comprising carbon monoxide and hydrogen and returning to process step c).

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